Urea (multi)-urethane (meth)acrylate-silane compositions and articles including the same

ABSTRACT

Compositions of matter described as urea (multi)-urethane (meth)acrylate-silanes having the general formula R A —NH—C(O)—N(R 4 )—R 11 —[O—C(O)NH—R S ] n , or R S —NH—C(O)—N(R 4 )—R 11 —[O—C(O)NH—R A ] n . Also described are articles including a substrate, a base (co)polymer layer on a major surface of the substrate, an oxide layer on the base (co)polymer layer; and a protective (co)polymer layer on the oxide layer, the protective (co)polymer layer including the reaction product of at least one urea (multi)-urethane (meth)acrylate-silane precursor compound. The substrate may be a (co)polymer film or an electronic device such as an organic light emitting device, electrophoretic light emitting device, liquid crystal display, thin film transistor, or combination thereof. Methods of making such urea (multi)-urethane (meth)acrylate-silane precursor compounds, and their use in composite films and electronic devices are also described. Methods of using multilayer composite films as barrier films in articles selected from solid state lighting devices, display devices, and photovoltaic devices are also described.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.15/871,593, filed Jan. 15, 2018, which is a continuation of U.S.application Ser. No. 14/417831, filed Jan. 28, 2015, which is a U.S. 371Application based on PCT/US2013/028510, filed on Mar. 1, 2013, whichclaims the benefit of U.S. Provisional Application Nos. 61/681,003,61/681,008, 61/681,023, 61/681,051, and 61/680,995, all filed Aug. 8,2012, the disclosures of which are incorporated by reference in theirentirety herein.

FIELD

The present disclosure relates to the preparation of urea(multi)-urethane (meth)acrylate-silane compounds and their use and theiruse in preparing composite barrier assemblies. More particularly, thedisclosure relates to vapor-deposited protective (co)polymer layersincluding the reaction product of at least one urea (multi)-urethane(meth)acrylate-silane precursor compound, used in multilayer compositebarrier assemblies in articles and barrier films.

BACKGROUND

Inorganic or hybrid inorganic/organic layers have been used in thinfilms for electrical, packaging and decorative applications. Theselayers can provide desired properties such as mechanical strength,thermal resistance, chemical resistance, abrasion resistance, moisturebarriers, and oxygen barriers. Highly transparent multilayer barriercoatings have also been developed to protect sensitive materials fromdamage due to water vapor. The moisture sensitive materials can beelectronic components such as organic, inorganic, and hybridorganic/inorganic semiconductor devices. The multilayer barrier coatingscan be deposited directly on the moisture sensitive material, or can bedeposited on a flexible transparent substrate such as a (co)polymerfilm.

Multilayer barrier coatings can be prepared by a variety of productionmethods. These methods include liquid coating techniques such assolution coating, roll coating, dip coating, spray coating, spincoating; and dry coating techniques such as Chemical Vapor Deposition(CVD), Plasma Enhanced Chemical Vapor Deposition (PECVD), sputtering andvacuum processes for thermal evaporation of solid materials. Oneapproach for multilayer barrier coatings has been to produce multilayeroxide coatings, such as aluminum oxide or silicon oxide, interspersedwith thin (co)polymer film protective layers. Each oxide/(co)polymerfilm pair is often referred to as a “dyad”, and the alternatingoxide/(co)polymer multilayer construction can contain several dyads toprovide adequate protection from moisture and oxygen. Examples of suchtransparent multilayer barrier coatings and processes can be found, forexample, in U.S. Pat. No. 5,440,446 (Shaw et al.); U.S. Pat. No.5,877,895 (Shaw et al.); U.S. Pat. No. 6,010,751 (Shaw et al.); U.S.Pat. No. 7,018,713 (Padiyath et al.); and U.S. Pat. No. 6,413,645 (Graffet al.).

SUMMARY

In one aspect, the present disclosure features compositions of matterincluding at least one urea (multi)-urethane (meth)acrylate-silanecompound of the formula R_(A)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(S)]_(n).R_(A) is a (meth)acryl containing group of the formula R¹¹—(A)_(n), inwhich R¹¹ is a polyvalent alkylene, arylene, alkarylene, or aralkylenegroup, said alkylene, arylene, alkarylene, or aralkylene groupsoptionally containing one or more catenary oxygen atom, A is a(meth)acryl group comprising the formula X²—C(O)—C(R³)═CH_(2,) in whichX² is —O, —S, or —NR³, R³ is independently H, or C₁-C_(4,) and n=1 to 5.Additionally, R⁴ is H, C₁ to C₆ alkyl, or C₁ to C₆ cycloalkyl. R_(S) isa silane containing group of the formula —R¹—[Si(Y_(p))(R²)_(3-p)]_(q),in which R¹ is a polyvalent alkylene, arylene, alkarylene, or aralkylenegroup, said alkylene, arylene, alkarylene, or aralkylene groupsoptionally containing one or more catenary oxygen atoms, Y is ahydrolysable group, R² is a monovalent alkyl or aryl group, and p is1,2, or 3.

In a related aspect, the present disclosure features compositions ofmatter including at least urea (multi)-urethane (meth)acrylate-silanecompound of the formula R_(S)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(A)]_(n).R_(S) is a silane containing group of the formula—R¹—Si(Y_(p))(R²)_(3-p), in which R¹ is a polyvalent alkylene, arylene,alkarylene, or aralkylene group, said alkylene, arylene, alkarylene, oraralkylene groups optionally containing one or more catenary oxygenatoms, Y is a hydrolysable group, R² is a monovalent alkyl or arylgroup, and p is 1,2, or 3. Additionally, R⁴ is H, C₁ to C₆ alkyl, or C₁to C₆ cycloalkyl. R_(A) is a (meth)acryl group containing group of theformula R¹¹-(A)_(n) , in which R¹¹ is a polyvalent alkylene, arylene,alkarylene, or aralkylene group, said alkylene, arylene, alkarylene, oraralkylene group optionally containing one or more catenary oxygen atom,A is a (meth)acryl containing group of the formula X²—C(O)—C(R³)═CH_(2,)in which X² is —O, —S, or —NR³, R³ is independently H, or C₁-C_(4,) andn=1 to 5.

In any of the foregoing embodiments, each hydrolysable group Y isindependently selected from an alkoxy group, an acetate group, anaryloxy group, and a halogen. In some particular exemplary embodimentsof the foregoing, at least some of the hydrolysable groups Y are alkoxygroups.

In another aspect, the present disclosure describes an article includinga substrate selected from a (co)polymeric film or an electronic device,the electronic device further including an organic light emitting device(OLED), an electrophoretic light emitting device, a liquid crystaldisplay, a thin film transistor, a photovoltaic device, or a combinationthereof; a base (co)polymer layer on a major surface of the substrate; abase (co)polymer layer on a major surface of the substrate; an oxidelayer on the base (co)polymer layer; and a protective (co)polymer layeron the oxide layer, wherein the protective (co)polymer layer comprisesthe reaction product of at least one of the foregoing urea(multi)-urethane (meth)acrylate-silane precursor compound of the formulaR_(A)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(S)]_(n), orR_(S)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(A)]_(n), as described above.

In any of the foregoing articles, each hydrolysable group Y isindependently selected from an alkoxy group, an acetate group, anaryloxy group, and a halogen. In some particular exemplary embodimentsof the foregoing articles, at least some of the hydrolysable groups Yare alkoxy groups.

In additional exemplary embodiments of any of the foregoing articles,the article further includes a multiplicity of alternating layers of theoxide layer and the protective (co)polymer layer on the base (co)polymerlayer.

Some exemplary embodiments of the present disclosure provide compositebarrier assemblies, for example composite barrier films. Thus, in someexemplary embodiments of the foregoing articles, the substrate is aflexible transparent (co)polymeric film, optionally wherein thesubstrate comprises polyethylene terephthalate (PET), polyethylenenapthalate (PEN), heat stabilized PET, heat stabilized PEN,polyoxymethylene, polyvinylnaphthalene, polyetheretherketone, afluoro(co)polymer, polycarbonate, polymethylmethacrylate, poly α-methylstyrene, polysulfone, polyphenylene oxide, polyetherimide,polyethersulfone, polyamideimide, polyimide, polyphthalamide, orcombinations thereof. In other exemplary embodiments of any of theforegoing composite films, the base (co)polymer layer includes a(meth)acrylate smoothing layer.

In further exemplary embodiments of any of the foregoing articles, theoxide layer includes at least one oxide, nitride, carbide or boride ofatomic elements selected from Groups IIA, IIIA, IVA, VA, VIA, VIIA, IB,or IIB, metals of Groups IIIB, IVB, or VB, rare-earth metals, or acombination or mixture thereof. In some exemplary embodiments of any ofthe foregoing articles, the article further includes an oxide layerapplied to the protective (co)polymer layer, optionally wherein theoxide layer includes silicon aluminum oxide.

In a further aspect, the disclosure describes methods of using acomposite barrier film as described above in an article selected from aphotovoltaic device, a solid state lighting device, a display device,and combinations thereof. Exemplary solid state lighting devices includesemiconductor light-emitting diodes (SLEDs, more commonly known asLEDs), organic light-emitting diodes (OLEDs), or polymer light-emittingdiodes (PLEDs). Exemplary display devices include liquid crystaldisplays, OLED displays, and quantum dot displays.

In an additional aspect, the disclosure describes a process including:(a) applying a base (co)polymer layer to a major surface of a substrate,(b) applying an oxide layer on the base (co)polymer layer, and (c)depositing on the oxide layer a protective (co)polymer layer, whereinthe protective (co)polymer layer includes a (co)polymer formed as thereaction product of at least one of the foregoing urea (multi)-urethane(meth)acrylate-silane precursor compound of the formulaR_(A)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(S)]_(n), orR_(S)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(A)]_(n), as previously described.The substrate is selected from a (co)polymeric film or an electronicdevice, the electronic device further including an organic lightemitting device (OLED), an electrophoretic light emitting device, aliquid crystal display, a thin film transistor, a photovoltaic device,or a combination thereof.

In some exemplary embodiments of the foregoing process, the at least oneurea (multi)-urethane (meth)acrylate-silane precursor compound undergoesa chemical reaction to form the protective (co)polymer layer at least inpart on the oxide layer. Optionally, the chemical reaction is selectedfrom a free radical polymerization reaction, and a hydrolysis reaction.In any of the foregoing processes, each hydrolysable group Y isindependently selected from an alkoxy group, an acetate group, anaryloxy group, and a halogen. In some particular exemplary embodimentsof the foregoing articles, at least some of the hydrolysable groups Yare chlorine.

In some particular exemplary embodiments of any of the foregoingprocesses, step (a) includes (i) evaporating a base (co)polymerprecursor, (ii) condensing the evaporated base (co)polymer precursoronto the substrate, and (iii) curing the evaporated base (co)polymerprecursor to form the base (co)polymer layer. In certain such exemplaryembodiments, the base (co)polymer precursor includes a (meth)acrylatemonomer.

In certain particular exemplary embodiments of any of the foregoingprocesses, step (b) includes depositing an oxide onto the base(co)polymer layer to form the oxide layer.

Depositing is achieved using sputter deposition, reactive sputtering,chemical vapor deposition, or a combination thereof. In some particularexemplary embodiments of any of the foregoing processes, step (b)includes applying a layer of an inorganic silicon aluminum oxide to thebase (co)polymer layer. In further exemplary embodiments of any of theforegoing processes, the process further includes sequentially repeatingsteps (b) and (c) to form a multiplicity of alternating layers of theprotective (co)polymer layer and the oxide layer on the base (co)polymerlayer.

In additional exemplary embodiments of any of the foregoing processes,step (c) further includes at least one of co-evaporating the at leastone urea (multi)-urethane (meth)acrylate-silane precursor compound witha (meth)acrylate compound from a liquid mixture, or sequentiallyevaporating the at least one urea (multi)-urethane (meth)acrylate-silaneprecursor compound and a (meth)acrylate compound from separate liquidsources. Optionally, the liquid mixture includes no more than about 10wt. % of the urea (multi)-urethane (meth)acrylate-silane precursorcompound. In further exemplary embodiments of such processes, step (c)further includes at least one of co-condensing the urea (multi)-urethane(meth)acrylate-silane precursor compound with the (meth)acrylatecompound onto the oxide layer, or sequentially condensing the urea(multi)-urethane (meth)acrylate-silane precursor compound and the(meth)acrylate compound on the oxide layer.

In further exemplary embodiments of any of the foregoing processes,reacting the urea (multi)-urethane (meth)acrylate-silane precursorcompound with the (meth)acrylate compound to form a protective(co)polymer layer on the oxide layer occurs at least in part on theoxide layer.

Some exemplary embodiments of the present disclosure provide compositebarrier assemblies, articles or barrier films which exhibit improvedmoisture resistance when used in moisture exposure applications.Exemplary embodiments of the disclosure can enable the formation ofbarrier assemblies, articles or barrier films that exhibit superiormechanical properties such as elasticity and flexibility yet still havelow oxygen or water vapor transmission rates.

Exemplary embodiments of barrier assemblies or barrier films accordingto the present disclosure are preferably transmissive to both visibleand infrared light. Exemplary embodiments of barrier assemblies orbarrier films according to the present disclosure are also typicallyflexible. Exemplary embodiments of barrier assemblies or barrier filmsaccording to the present disclosure generally do not exhibitdelamination or curl that can arise from thermal stresses or shrinkagein a multilayer structure. The properties of exemplary embodiments ofbarrier assemblies or barrier films disclosed herein typically aremaintained even after high temperature and humidity aging.

Various aspects and advantages of exemplary embodiments of the presentdisclosure have been summarized. The above Summary is not intended todescribe each illustrated embodiment or every implementation of thepresent invention. Further features and advantages are disclosed in theembodiments that follow. The Drawings and the Detailed Description thatfollow more particularly exemplify certain preferred embodiments usingthe principles disclosed herein.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings are incorporated in and constitute a part ofthis specification and, together with the description, explain theadvantages and principles of exemplary embodiments of the presentdisclosure.

FIG. 1 is a diagram illustrating an exemplary moisture-resistant barrierassembly in an article or film having a vapor-depositedadhesion-promoting coating according to an exemplary embodiment of thepresent disclosure; and

FIG. 2 is a diagram illustrating an exemplary process and apparatus formaking a barrier film according to an exemplary embodiment of thepresent disclosure.

Like reference numerals in the drawings indicate like elements. Thedrawings herein are not drawn to scale, and in the drawings, theillustrated elements are sized to emphasize selected features.

DETAILED DESCRIPTION

Glossary

Certain terms are used throughout the description and the claims that,while for the most part are well known, may require some explanation. Itshould understood that, as used herein,

The words “a”, “an”, and “the” are used interchangeably with “at leastone” to mean one or more of the elements being described.

By using words of orientation such as “atop”, “on”, “covering”,“uppermost”, “underlying” and the like for the location of variouselements in the disclosed coated articles, we refer to the relativeposition of an element with respect to a horizontally-disposed,upwardly-facing substrate. It is not intended that the substrate orarticles should have any particular orientation in space during or aftermanufacture.

By using the term “overcoated” to describe the position of a layer withrespect to a substrate or other element of a barrier assembly in anarticle or film of the disclosure, we refer to the layer as being atopthe substrate or other element, but not necessarily contiguous to eitherthe substrate or the other element.

By using the term “separated by” to describe the position of a(co)polymer layer with respect to two inorganic barrier layers, we referto the (co)polymer layer as being between the inorganic barrier layersbut not necessarily contiguous to either inorganic barrier layer.

The terms “barrier assembly,” “barrier film” or “barrier layer” refersto an assembly, film or layer which is designed to be impervious tovapor, gas or aroma migration. Exemplary gases and vapors that may beexcluded include oxygen and/or water vapor.

The term “(meth)acrylate” with respect to a monomer, oligomer orcompound means a vinyl-functional alkyl ester formed as the reactionproduct of an alcohol with an acrylic or a methacrylic acid.

The term “polymer” or “(co)polymer” includes homopolymers andcopolymers, as well as homopolymers or copolymers that may be formed ina miscible blend, e.g., by coextrusion or by reaction, including, e.g.,transesterification. The term “copolymer” includes both random and blockcopolymers.

The term “cure” refers to a process that causes a chemical change, e.g.,a reaction via consumption of water, to solidify a film layer orincrease its viscosity.

The term “cross-linked” (co)polymer refers to a (co)polymer whose(co)polymer chains are joined together by covalent chemical bonds,usually via cross-linking molecules or groups, to form a network(co)polymer. A cross-linked (co)polymer is generally characterized byinsolubility, but may be swellable in the presence of an appropriatesolvent.

The term “cured (co)polymer” includes both cross-linked anduncross-linked (co)polymers.

The term “T_(g)” refer to the glass transition temperature of a cured(co)polymer when evaluated in bulk rather than in a thin film form. Ininstances where a (co)polymer can only be examined in thin film form,the bulk form T_(g) can usually be estimated with reasonable accuracy.Bulk form T_(g) values usually are determined by evaluating the rate ofheat flow vs. temperature using differential scanning calorimetry (DSC)to determine the onset of segmental mobility for the (co)polymer and theinflection point (usually a second-order transition) at which the(co)polymer can be said to change from a glassy to a rubbery state. Bulkform T_(g) values can also be estimated using a dynamic mechanicalthermal analysis (DMTA) technique, which measures the change in themodulus of the (co)polymer as a function of temperature and frequency ofvibration.

By using the term “visible light-transmissive” support, layer, assemblyor device, we mean that the support, layer, assembly or device has anaverage transmission over the visible portion of the spectrum, T_(vis),of at least about 20%, measured along the normal axis.

The term “metal” includes a pure metal (i.e. a metal in elemental formsuch as, for example silver, gold, platinum, and the like) or a metalalloy.

The term “vapor coating” or “vapor depositing” means applying a coatingto a substrate surface from a vapor phase, for example, by evaporatingand subsequently depositing onto the substrate surface a precursormaterial to the coating or the coating material itself. Exemplary vaporcoating processes include, for example, physical vapor deposition (PVD),chemical vapor deposition (CVD), and combinations thereof.

Various exemplary embodiments of the disclosure will now be describedwith particular reference to the Drawings. Exemplary embodiments of thepresent disclosure may take on various modifications and alterationswithout departing from the spirit and scope of the disclosure.Accordingly, it is to be understood that the embodiments of the presentdisclosure are not to be limited to the following described exemplaryembodiments, but are to be controlled by the limitations set forth inthe claims and any equivalents thereof.

Identification of a Problem to be Solved

Flexible barrier assemblies or films are desirable for electronicdevices whose components are sensitive to the ingress of water vapor. Amultilayer barrier assembly or film may provide advantages over glass asit is flexible, light-weight, durable, and enables low cost continuousroll-to-roll processing.

Each of the known methods for producing a multilayer barrier assembly orfilm has limitations. Chemical deposition methods (CVD and PECVD) formvaporized metal alkoxide precursors that undergo a reaction, whenadsorbed on a substrate, to form inorganic coatings. These processes aregenerally limited to low deposition rates (and consequently low linespeeds), and make inefficient use of the alkoxide precursor (much of thealkoxide vapor is not incorporated into the coating). The CVD processalso requires high substrate temperatures, often in the range of300-500° C., which may not be suitable for (co)polymer substrates.

Vacuum processes such as thermal evaporation of solid materials (e.g.,resistive heating or e-beam heating) also provide low metal oxidedeposition rates. Thermal evaporation is difficult to scale up for rollwide web applications requiring very uniform coatings (e.g., opticalcoatings) and can require substrate heating to obtain quality coatings.Additionally, evaporation/sublimation processes can require ion-assist,which is generally limited to small areas, to improve the coatingquality.

Sputtering has also been used to form metal oxide layers. While thedeposition energy of the sputter process used for forming the barrieroxide layer is generally high, the energy involved in depositing the(meth)acrylate layers is generally low. As a result the (meth)acrylatelayer typically does not have good adhesive properties with the layerbelow it, for example, an inorganic barrier oxide sub-layer. To increasethe adhesion level of the protective (meth)acrylate layer to the barrieroxide, a thin sputtered layer of silicon sub-oxide is known to be usefulin the art. If the silicon sub oxide layer is not included in the stack,the protective (meth)acrylate layer has poor initial adhesion to thebarrier oxide. The silicon sub oxide layer sputter process must becarried out with precise power and gas flow settings to maintainadhesion performance. This deposition process has historically beensusceptible to noise resulting in varied and low adhesion of theprotective (meth)acrylate layer. It is therefore desirable to eliminatethe need for a silicon sub oxide layer in the final barrier constructfor increased adhesion robustness and reduction of process complexity.

Even when the “as deposited” adhesion of the standard barrier stack isinitially acceptable, the sub oxide and protective (meth)acrylate layerhas demonstrated weakness when exposed to accelerated aging conditionsof 85° C./85% relative humidity (RH). This inter-layer weakness canresult in premature delamination of the barrier film from the devices itis intended to protect. It is desirable that the multi-layerconstruction improves upon and maintains initial adhesion levels whenaged in 85° C. and 85% RH.

One solution to this problem is to use what is referred to as a “tie”layer of particular elements such chromium, zirconium, titanium, siliconand the like, which are often sputter deposited as a mono- or thin-layerof the material either as the element or in the presence of small amountof oxygen. The tie layer element can then form chemical bonds to boththe substrate layer, an oxide, and the capping layer, a (co)polymer.

Tie layers are generally used in the vacuum coating industry to achieveadhesion between layers of differing materials. The process used todeposit the layers often requires fine tuning to achieve the right layerconcentration of tie layer atoms. The deposition can be affected byslight variations in the vacuum coating process such as fluctuation invacuum pressure, out-gassing, and cross contamination from otherprocesses resulting in variation of adhesion levels in the product. Inaddition, tie layers often do not retain their initial adhesion levelsafter exposure to water vapor. A more robust solution for adhesionimprovement in barrier assembly in an article or films is desirable.

Discovery of a Solution to the Problem

We have surprisingly discovered that a composite film comprising aprotective (co)polymer layer comprising the reaction product of at leastone urea (multi)-urethane (meth)acrylate-silane precursor compound asdescribed further below, improves the adhesion and moisture barrierperformance of a multilayer composite barrier assembly in an article orfilm. These multilayer composite barrier assemblies in articles or filmshave a number of applications in the photovoltaic, display, lighting,and electronic device markets as flexible replacements for glassencapsulating materials.

In exemplary embodiments of the present disclosure, the desiredtechnical effects and solution to the technical problem to obtainimproved multilayer composite barrier assemblies in articles or filmswere obtained by chemically modifying the compositions used in theprocess for applying (e.g., by vapor coating) a protective (co)polymerlayer to an article or film to achieve, in some exemplary embodiments:

-   -   1) a robust chemical bond with an inorganic oxide surface,    -   2) a robust chemical bond to the (meth)acrylate coating through        (co)polymerization, and    -   3) the maintenance of some of the physical properties of the        modified molecules (e.g., boiling point, vapor pressure, and the        like) such that they can be co-evaporated with a bulk        (meth)acrylate material.        Multilayer Composite Barrier Assemblies or Films

Thus, in exemplary embodiments, the disclosure describes a multilayercomposite barrier assembly in an article or film comprising a substrate,a base (co)polymer layer on a major surface of the substrate, an oxidelayer on the base (co)polymer layer; and a protective (co)polymer layeron the oxide layer, the protective (co)polymer layer comprising thereaction product of at least one urea (multi)-urethane(meth)acrylate-silane precursor compound of the formulaR_(A)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(S)]_(n), orR_(S)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(A)]_(n), as described furtherbelow.

An optional inorganic layer, which preferably is an oxide layer, can beapplied over the protective (co)polymer layer. Presently preferredinorganic layers comprise at least one of silicon aluminum oxide orindium tin oxide.

In certain exemplary embodiments, the composite film is a multilayercomposite barrier assembly in an article or film comprising a pluralityof alternating layers of the oxide layer and the protective (co)polymerlayer on the base (co)polymer layer. The oxide layer and protective(co)polymer layer together form a “dyad”, and in one exemplaryembodiment, the barrier assembly in an article or film can include morethan one dyad, forming a multilayer barrier assembly in an article orfilm. Each of the oxide layers and/or protective (co)polymer layers inthe multilayer barrier assembly in an article or film (i.e. includingmore than one dyad) can be the same or different. An optional inorganiclayer, which preferably is an oxide layer, can be applied over theplurality of alternating layers or dyads.

Turning to the drawings, FIG. 1 is a diagram of an exemplary barrierassembly in an article or film 10 having a moisture resistant coatingcomprising a single dyad. Film 10 includes layers arranged in thefollowing order: a substrate 12; a base (co)polymer layer 14; an oxidelayer 16; a protective (co)polymer layer 18 comprising the reactionproduct of at least one urea (multi)-urethane (meth)acrylate-silaneprecursor compound as described herein; and an optional oxide layer 20.Oxide layer 16 and protective (co)polymer layer 18 together form a dyadand, although only one dyad is shown, film 10 can include additionaldyads of alternating oxide layer 16 and protective (co)polymer layer 18between substrate 10 and the uppermost dyad.

In certain exemplary embodiments, the composite barrier assembly in anarticle or film comprises a plurality of alternating layers of the oxidelayer and the protective (co)polymer layer on the base (co)polymerlayer. The oxide layer and protective (co)polymer layer together form a“dyad”, and in one exemplary embodiment, the barrier assembly in anarticle or film can include more than one dyad, forming a multilayerbarrier assembly in an article or film. Each of the oxide layers and/orprotective (co)polymer layers in the multilayer barrier assembly in anarticle or film (i.e. including more than one dyad) can be the same ordifferent. An optional inorganic layer, which preferably is an oxidelayer, can be applied over the plurality of alternating layers or dyads.

In some exemplary embodiments, protective (co)polymer layer 18comprising the reaction product of at least one urea (multi)-urethane(meth)acrylate-silane precursor compound as described further below,improves the moisture resistance of film 10 and the peel strengthadhesion of protective (co)polymer layer 18 to the underlying oxidelayer, leading to improved adhesion and delamination resistance withinthe further barrier stack layers, as explained further below. Presentlypreferred materials for use in the barrier assembly in an article orfilm 10 are also identified further below, and in the Examples.

Protective (Co)polymer Layers

The present disclosure describes protective (co)polymer layers used incomposite films (i.e., as barrier films) useful in reducing oxygenand/or water vapor barrier transmission when used as packagingmaterials, for example, to package electronic devices. Each protective(co)polymer layer includes in its manufacture at least one compositionof matter described herein as a urea (multi)-urethane(meth)acrylate-silane precursor compound, the reaction product thereofforms a (co)polymer, as described further below.

Thus, in some exemplary embodiments, the present disclosure describes acomposite film comprising a substrate, a base (co)polymer layer on amajor surface of the substrate, an oxide layer on the base (co)polymerlayer, and a protective (co)polymer layer on the oxide layer, whereinthe protective (co)polymer layer comprises the reaction product of atleast one of the foregoing urea (multi)-urethane (meth)acrylate-silaneprecursor compounds of the formulaR_(A)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(S)]_(n), orR_(S)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(A)]_(n), as described furtherbelow.

Composite Barrier Assembly or Barrier Film Materials

The present disclosure describes protective (co)polymer layerscomprising the reaction product of at least one urea (multi)-urethane(meth)acrylate-silane precursor compound having the general formulaR_(A)—NH—C(O)—N(R⁴)R¹¹—[O—C(O)NH—R_(S)]_(n), orR_(S)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(A)]_(n), as described furtherbelow. Among other things, (co)polymer layers comprising such reactionproduct(s) of at least one urea (multi)-urethane (meth)acrylate-silaneprecursor compound are useful for improving the interlayer adhesion ofcomposite barrier assembly in an article or films.

Urea (Multi)-Urethane (Meth)acrylate-Silane Precursor Compounds

Thus, in one exemplary embodiment, the present disclosure describes newcompositions of matter comprising at least one urea (multi)-urethane(meth)acrylate-silane precursor compound of the formulaR_(A)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(S)]_(n). R_(A) is a (meth)acrylcontaining group of the formula R¹¹-(A)_(n), in which R¹¹ is apolyvalent alkylene, arylene, alkarylene, or aralkylene group, saidalkylene, arylene, alkarylene, or aralkylene groups optionallycontaining one or more catenary oxygen atom, A is a (meth)acryl groupcomprising the formula X²—C(O)—C(R³)═CH_(2,) in which X² is —O, —S, or—NR³, R³ is independently H, or C₁-C_(4,) and n=1 to 5. Additionally, R⁴is H, C₁ to C₆ alkyl, or C₁ to C₆ cycloalkyl. R_(S) is a silanecontaining group of the formula —R¹—[Si(Y_(p))(R²)_(3-p)]_(q), in whichR¹ is a polyvalent alkylene, arylene, alkarylene, or aralkylene group,said alkylene, arylene, alkarylene, or aralkylene groups optionallycontaining one or more catenary oxygen atoms, Y is a hydrolysable group,R² is a monovalent alkyl or aryl group, and p is 1,2, or 3.

In a related embodiment, the present disclosure describes newcompositions of matter comprising at least one urea (multi)-urethane(meth)acrylate-silane precursor compound of the formulaR_(S)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(A)]_(n). R_(S) is a silanecontaining group of the formula —R¹-Si(Y_(p))(R²)_(3-p), in which R¹ isa polyvalent alkylene, arylene, alkarylene, or aralkylene group, saidalkylene, arylene, alkarylene, or aralkylene groups optionallycontaining one or more catenary oxygen atoms, Y is a hydrolysable group,R² is a monovalent alkyl or aryl group, and p is 1,2, or 3.Additionally, R⁴ is H, C₁ to C₆ alkyl, or C₁ to C₆ cycloalkyl. R_(A) isa (meth)acryl group containing group of the formula R¹¹-(A)_(n), inwhich R¹¹ is a polyvalent alkylene, arylene, alkarylene, or aralkylenegroup, said alkylene, arylene, alkarylene, or aralkylene groupoptionally containing one or more catenary oxygen atom, A is a(meth)acryl containing group of the formula X²—C(O)—C(R³)═CH_(2,) inwhich X² is —O, —S, or —NR³, R³ is independently H, or C₁-C_(4,) and n=1to 5.

In any of the foregoing embodiments, each hydrolysable group Y isindependently selected from an alkoxy group, an acetate group, anaryloxy group, and a halogen. In some particular exemplary embodimentsof the foregoing, at least some of the hydrolysable groups Y are alkoxygroups.

Urea (multi)-urethane (meth)acrylate-silane precursor compounds of theformula R_(A)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(S)]_(n) may be formed byreacting a primary or secondary amine having one or more alcohol groupsis reacted in a first step with a (meth)acrylated material havingisocyanate functionality, either neat or in a solvent, and optionallywith a catalyst, such as a tin compound, to accelerate the reaction. Thefollowing reaction equation is illustrative:R_(A)-NCO+H(R⁴)N—R¹¹—[OH]_(n)→R_(A)—NH—C(O)—N(R⁴)—R¹¹—[OH]_(n)   (1)

Conditions can be used to selectively react the primary or secondaryamine functional group of the primary or secondary amine having one ormore alcohol groups with the isocyanate group of the (meth)acrylatedmaterial having isocyanate functionality. Methods used in obtaining thedesired intermediate R_(A)—NH—C(O)—N(R⁴)—R¹¹—[OH]_(n) includesimultaneous addition of both the R_(A)-NCO and the H(R⁴)N—R¹¹—[OH]_(n),use of low temperatures, and use of tin catalysts such asdibutyltindilaurate.

In the second step, this intermediate with urea, acrylate, and alcoholfunctional groups is then reacted with an isocyanate functional silanecompound, either neat or in a solvent, and optionally with a catalyst,such as a tin compound, to accelerate the reaction, to provide thematerials of the formula R_(A)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(S)]_(n) .

Urea (multi)-urethane (meth)acrylate-silane precursor compounds of theformula R_(S)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(A)]_(n) may be formed byreacting a primary or secondary amine having one or more alcohol groupsis reacted in a first step with an isocyanate functional silanecompound, either neat or in a solvent, and optionally with a catalyst,such as a tin compound, to accelerate the reaction. The followingequation is illustrative:R_(S)—NCO+H(R⁴)N—R¹¹—[OH]_(n) →R_(S)—NH—C(O)—N(R⁴)—R¹¹—[OH]_(n)   (2)

In the second step, this intermediate with urea, silane, and alcoholfunctional groups is reacted with a (meth)acrylated material havingisocyanate functionality, either neat or in a solvent, and optionallywith a catalyst, such as a tin compound, to accelerate the reaction, toprovide materials of the formulaR_(S)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(A)]_(n).

(Meth)acrylated materials of the general formula R_(A)-NCO havingisocyanate functionality include 3-isocyanatoethyl methacrylate,3-isocyanatoethyl methacrylate, and 1,1-bis(acryloyloxymethyl) ethylisocyanate.

Primary or secondary amines having one or more alcohol groups of thegeneral formula H(R⁴)N—R¹¹—[OH]_(n) include ethanolamine,diethanolamine, N-methyl-ethanolamine, and2-amino-2-ethyl-1,3-propanediol, among others.

Examples of silane compounds having isocyanate functionality of theformula R_(S)—NCO include 3-triethoxysilylpropyl isocyanate, and3-trimethoxysilylpropyl isocyanate. Additional information about thepreparation of urethanes can be found in Polyurethanes: Chemistry andTechnology, Saunders and Frisch, Interscience Publishers (New York,1963(Part I) and 1964 (Part II).

The molecular weight of the urea (multi)-urethane (meth)acrylate-silaneprecursor compound is in the range where sufficient vapor pressure atvacuum process conditions is effective to carry out evaporation and thensubsequent condensation to a thin liquid film. The molecular weights arepreferably less than about 2,000 Da, more preferably less than 1,000 Da,even more preferably less than 500 Da.

Preferably, the urea (multi)-urethane (meth)acrylate-silane precursorcompound is present at no more than 20% by weight (% wt.) of the vaporcoated mixture; more preferably no more than 19%, 18%, 17%, 16%, 15%,14%, 13%, 12%, 11%, and even more preferably 10%, 9%, 8%, 7%, 6%, 5%,4%, 3%, 2% or even 1% wt. of the vapor deposited mixture.

An optional inorganic layer, which preferably is an oxide layer, can beapplied over the protective (co)polymer layer. Presently preferredinorganic layers comprise at least one of silicon aluminum oxide orindium tin oxide.

Substrates

The substrate 12 is selected from a (co)polymeric film or an electronicdevice, the electronic device further including an organic lightemitting device (OLED), an electrophoretic light emitting device, aliquid crystal display, a thin film transistor, a photovoltaic device,or a combination thereof.

Typically, the electronic device substrate is a moisture sensitiveelectronic device. The moisture sensitive electronic device can be, forexample, an organic, inorganic, or hybrid organic/inorganicsemiconductor device including, for example, a photovoltaic device suchas a copper indium gallium (di)selenide (CIGS) solar cell; a displaydevice such as an organic light emitting display (OLED), electrochromicdisplay, electrophoretic display, or a liquid crystal display (LCD) suchas a quantum dot LCD display; an OLED or other electroluminescent solidstate lighting device, or combinations thereof and the like.

In some exemplary embodiments, substrate 12 can be a flexible, visiblelight-transmissive substrate, such as a flexible light transmissive(co)polymeric film. In one presently preferred exemplary embodiment, thesubstrates are substantially transparent, and can have a visible lighttransmission of at least about 50%, 60%, 70%, 80%, 90% or even up toabout 100% at 550 nm.

Exemplary flexible light-transmissive substrates include thermoplastic(co)polymeric films including, for example, polyesters, polyacrylates(e.g., polymethyl methacrylate), polycarbonates, polypropylenes, high orlow density polyethylenes, polysulfones, polyether sulfones,polyurethanes, polyamides, polyvinyl butyral, polyvinyl chloride,fluoro(co)polymers (e.g., polyvinylidene difluoride andpolytetrafluoroethylene), polyethylene sulfide, and thermoset films suchas epoxies, cellulose derivatives, polyimide, polyimide benzoxazole andpolybenzoxazole.

Presently preferred (co)polymeric films comprise polyethyleneterephthalate (PET), polyethylene napthalate (PEN), heat stabilized PET,heat stabilized PEN, polyoxymethylene, polyvinylnaphthalene,polyetheretherketone, fluoro(co)polymer, polycarbonate,polymethylmethacrylate, poly α-methyl styrene, polysulfone,polyphenylene oxide, polyetherimide, polyethersulfone, polyamideimide,polyimide, polyphthalamide, or combinations thereof.

In some exemplary embodiments, the substrate can also be a multilayeroptical film (“MOF”), such as those described in U.S. Patent ApplicationPublication No. US 2004/0032658 A1. In one exemplary embodiment, thefilms can be prepared on a substrate including PET.

The (co)polymeric film can be heat-stabilized, using heat setting,annealing under tension, or other techniques that will discourageshrinkage up to at least the heat stabilization temperature when the(co)polymeric film is not constrained.

The substrate may have a variety of thicknesses, e.g., about 0.01 toabout 1 mm. The substrate may however be considerably thicker, forexample, when a self-supporting article is desired. Such articles canconveniently also be made by laminating or otherwise joining a disclosedfilm made using a flexible substrate to a thicker, inflexible or lessflexible supplemental support.

Base (co)Polymer Layer

Returning to FIG. 1, the base (co)polymer layer 14 can include any(co)polymer suitable for deposition in a thin film. In one aspect, forexample, the base (co)polymer layer 14 can be formed from variousprecursors, for example, (meth)acrylate monomers and/or oligomers thatinclude acrylates or methacrylates such as urethane acrylates, isobornylacrylate, dipentaerythritol pentaacrylates, epoxy acrylates, epoxyacrylates blended with styrene, di-trimethylolpropane tetraacrylates,diethylene glycol diacrylates, 1,3-butylene glycol diacrylate,pentaacrylate esters, pentaerythritol tetraacrylates, pentaerythritoltriacrylates, ethoxylated (3) trimethylolpropane triacrylates,ethoxylated (3) trimethylolpropane triacrylates, alkoxylatedtrifunctional acrylate esters, dipropylene glycol diacrylates, neopentylglycol diacrylates, ethoxylated (4) bisphenol a dimethacrylates,cyclohexane dimethanol diacrylate esters, isobornyl methacrylate, cyclicdiacrylates and tris (2-hydroxy ethyl) isocyanurate triacrylate,acrylates of the foregoing methacrylates and methacrylates of theforegoing acrylates. Preferably, the base (co)polymer precursorcomprises a (meth)acrylate monomer.

The base (co)polymer layer 14 can be formed by applying a layer of amonomer or oligomer to the substrate and cross-linking the layer to formthe (co)polymer in situ, e.g., by flash evaporation and vapor depositionof a radiation-cross-linkable monomer, followed by cross-linking using,for example, an electron beam apparatus, UV light source, electricaldischarge apparatus or other suitable device. Coating efficiency can beimproved by cooling the substrate.

The monomer or oligomer can also be applied to the substrate 12 usingconventional coating methods such as roll coating (e.g., gravure rollcoating) or spray coating (e.g., electrostatic spray coating), thencross-linked as set out above. The base (co)polymer layer 14 can also beformed by applying a layer containing an oligomer or (co)polymer insolvent and drying the thus-applied layer to remove the solvent. PlasmaEnhanced Chemical Vapor Deposition (PECVD) may also be employed in somecases.

Preferably, the base (co)polymer layer 14 is formed by flash evaporationand vapor deposition followed by cross-linking in situ, e.g., asdescribed in U.S. Pat. No. 4,696,719 (Bischoff), U.S. Pat. No. 4,722,515(Ham), U.S. Pat. No. 4,842,893 (Yializis et al.), U.S. Pat. No.4,954,371 (Yializis), U.S. Pat. No. 5,018,048 (Shaw et al.), U.S. Pat.No. 5,032,461(Shaw et al.), U.S. Pat. No. 5,097,800 (Shaw et al.), U.S.Pat. No. 5,125,138 (Shaw et al.), U.S. Pat. No. 5,440,446 (Shaw et al.),U.S. Pat. No. 5,547,908 (Furuzawa et al.), U.S. Pat. No. 6,045,864(Lyons et al.), U.S. Pat. No. 6,231,939 (Shaw et al. and U.S. Pat. No.6,214,422 (Yializis); in PCT International Publication No. WO 00/26973(Delta V Technologies, Inc.); in D. G. Shaw and M. G. Langlois, “A NewVapor Deposition Process for Coating Paper and Polymer Webs”, 6thInternational Vacuum Coating Conference (1992); in D. G. Shaw and M. G.Langlois, “A New High Speed Process for Vapor Depositing Acrylate ThinFilms: An Update”, Society of Vacuum Coaters 36th Annual TechnicalConference Proceedings (1993); in D. G. Shaw and M. G. Langlois, “Use ofVapor Deposited Acrylate Coatings to Improve the Barrier Properties ofMetallized Film”, Society of Vacuum Coaters 37th Annual TechnicalConference Proceedings (1994); in D. G. Shaw, M. Roehrig, M. G. Langloisand C. Sheehan, “Use of Evaporated Acrylate Coatings to Smooth theSurface of Polyester and Polypropylene Film Substrates”, RadTech (1996);in J. Affinito, P. Martin, M. Gross, C. Coronado and E. Greenwell,“Vacuum Deposited Polymer/Metal Multilayer Films for OpticalApplication”, Thin Solid Films 270, 43-48 (1995); and in J. D. Affinito,M. E. Gross, C. A. Coronado, G. L. Graff, E. N. Greenwell and P. M.Martin, “Polymer-Oxide Transparent Barrier Layers”, Society of VacuumCoaters 39th Annual Technical Conference Proceedings (1996).

In some exemplary embodiments, the smoothness and continuity of the base(co)polymer layer 14 (and also each oxide layer 16 and protective(co)polymer layer 18) and its adhesion to the underlying substrate orlayer may be enhanced by appropriate pretreatment. Examples of asuitable pretreatment regimen include an electrical discharge in thepresence of a suitable reactive or non-reactive atmosphere (e.g.,plasma, glow discharge, corona discharge, dielectric barrier dischargeor atmospheric pressure discharge); chemical pretreatment or flamepretreatment. These pretreatments help make the surface of theunderlying layer more receptive to formation of the subsequently applied(co)polymeric (or inorganic) layer. Plasma pretreatment can beparticularly useful.

In some exemplary embodiments, a separate adhesion promotion layer whichmay have a different composition than the base (co)polymer layer 14 mayalso be used atop the substrate or an underlying layer to improveadhesion. The adhesion promotion layer can be, for example, a separate(co)polymeric layer or a metal-containing layer such as a layer ofmetal, metal oxide, metal nitride or metal oxynitride. The adhesionpromotion layer may have a thickness of a few nm (e.g., 1 or 2 nm) toabout 50 nm, and can be thicker if desired.

The desired chemical composition and thickness of the base (co)polymerlayer will depend in part on the nature and surface topography of thesubstrate. The thickness preferably is sufficient to provide a smooth,defect-free surface to which the subsequent oxide layer can be applied.For example, the base (co)polymer layer may have a thickness of a few nm(e.g., 2 or 3 nm) to about 5 micrometers, and can be thicker if desired.

As described elsewhere, the barrier film can include the oxide layerdeposited directly on a substrate that includes a moisture sensitivedevice, a process often referred to as direct encapsulation. Flexibleelectronic devices can be encapsulated directly with the gradientcomposition oxide layer. For example, the devices can be attached to aflexible carrier substrate, and a mask can be deposited to protectelectrical connections from the oxide layer deposition. The base(co)polymer layer 14, the oxide layer 16 and the protective (co)polymerlayer 18 can be deposited as described further below, and the mask canthen be removed, exposing the electrical connections.

Oxide Layers

The improved barrier film includes at least one oxide layer 16. Theoxide layer preferably comprises at least one inorganic material.Suitable inorganic materials include oxides, nitrides, carbides orborides of different atomic elements. Presently preferred inorganicmaterials included in the oxide layer comprise oxides, nitrides,carbides or borides of atomic elements from Groups IIA, IIIA, IVA, VA,VIA, VIIA, IB, or IIB, metals of Groups IIIB, IVB, or VB, rare-earthmetals, or combinations thereof. In some particular exemplaryembodiments, an inorganic layer, more preferably an inorganic oxidelayer, may be applied to the uppermost protective (co)polymer layer.Preferably, the oxide layer comprises silicon aluminum oxide or indiumtin oxide.

In some exemplary embodiments, the composition of the oxide layer maychange in the thickness direction of the layer, i.e. a gradientcomposition. In such exemplary embodiments, the oxide layer preferablyincludes at least two inorganic materials, and the ratio of the twoinorganic materials changes throughout the thickness of the oxide layer.The ratio of two inorganic materials refers to the relative proportionsof each of the inorganic materials. The ratio can be, for example, amass ratio, a volume ratio, a concentration ratio, a molar ratio, asurface area ratio, or an atomic ratio.

The resulting gradient oxide layer is an improvement over homogeneous,single component layers. Additional benefits in barrier and opticalproperties can also be realized when combined with thin, vacuumdeposited protective (co)polymer layers. A multilayer gradientinorganic-(co)polymer barrier stack can be made to enhance opticalproperties as well as barrier properties.

The first and second inorganic materials can be oxides, nitrides,carbides or borides of metal or nonmetal atomic elements, orcombinations of metal or nonmetal atomic elements. By “metal ornonmetal” atomic elements is meant atomic elements selected from theperiodic table Groups IIA, IIIA, IVA, VA, VIA, VIIA, IB, or IIB, metalsof Groups IIIB, IVB, or VB, rare-earth metals, or combinations thereof.Suitable inorganic materials include, for example, metal oxides, metalnitrides, metal carbides, metal oxynitrides, metal oxyborides, andcombinations thereof, e.g., silicon oxides such as silica, aluminumoxides such as alumina, titanium oxides such as titania, indium oxides,tin oxides, indium tin oxide (“ITO”), tantalum oxide, zirconium oxide,niobium oxide, aluminum nitride, silicon nitride, boron nitride,aluminum oxynitride, silicon oxynitride, boron oxynitride, zirconiumoxyboride, titanium oxyboride, and combinations thereof. ITO is anexample of a special class of ceramic materials that can becomeelectrically conducting with the proper selection of the relativeproportions of each elemental constituent. Silicon-aluminum oxide andindium tin oxide are presently preferred inorganic materials forming theoxide layer 16.

For purposes of clarity, the oxide layer 16 described in the followingdiscussion is directed toward a composition of oxides; however, it is tobe understood that the composition can include any of the oxides,nitrides, carbides, borides, oxynitrides, oxyborides and the likedescribed above.

In one embodiment of the oxide layer 16, the first inorganic material issilicon oxide, and the second inorganic material is aluminum oxide. Inthis embodiment, the atomic ratio of silicon to aluminum changesthroughout the thickness of the oxide layer, e.g., there is more siliconthan aluminum near a first surface of the oxide layer, graduallybecoming more aluminum than silicon as the distance from the firstsurface increases. In one embodiment, the atomic ratio of silicon toaluminum can change monotonically as the distance from the first surfaceincreases, i.e., the ratio either increases or decreases as the distancefrom the first surface increases, but the ratio does not both increaseand decrease as the distance from the first surface increases. Inanother embodiment, the ratio does not increase or decreasemonotonically, i.e. the ratio can increase in a first portion, anddecrease in a second portion, as the distance from the first surfaceincreases. In this embodiment, there can be several increases anddecreases in the ratio as the distance from the first surface increases,and the ratio is non-monotonic. A change in the inorganic oxideconcentration from one oxide species to another throughout the thicknessof the oxide layer 16 results in improved barrier performance, asmeasured by water vapor transmission rate.

In addition to improved barrier properties, the gradient composition canbe made to exhibit other unique optical properties while retainingimproved barrier properties. The gradient change in composition of thelayer produces corresponding change in refractive index through thelayer. The materials can be chosen such that the refractive index canchange from high to low, or vice versa. For example, going from a highrefractive index to a low refractive index can allow light traveling inone direction to easily pass through the layer, while light travellingin the opposite direction may be reflected by the layer. The refractiveindex change can be used to design layers to enhance light extractionfrom a light emitting device being protected by the layer. Therefractive index change can instead be used to pass light through thelayer and into a light harvesting device such as a solar cell. Otheroptical constructions, such as band pass filters, can also beincorporated into the layer while retaining improved barrier properties.

In order to promote silane bonding to the oxide surface, it may bedesirable to form hydroxyl silanol (Si—OH) groups on a freshly sputterdeposited silicon dioxide (SiO₂) layer. The amount of water vaporpresent in a multi-process vacuum chamber can be controlled sufficientlyto promote the formation of Si—OH groups in high enough surfaceconcentration to provide increased bonding sites. With residual gasmonitoring and the use of water vapor sources the amount of water vaporin a vacuum chamber can be controlled to ensure adequate generation ofSi—OH groups.

Process for Making Articles Including Barrier Assemblies or BarrierFilms

In other exemplary embodiments, the disclosure describes a process, e.g.for making a barrier film on a (co)polymer film substrate or for makingan article by depositing a multilayer composite barrier assembly on anelectronic device substrate, the process comprising: (a) applying a base(co)polymer layer to a major surface of a substrate, (b) applying anoxide layer on the base (co)polymer layer, and (c) depositing on theoxide layer a protective (co)polymer layer, wherein the protective(co)polymer layer comprises a (co)polymer formed as the reaction productof at least one of the foregoing urea (multi)-urethane(meth)acrylate-silane precursor compounds of the formulaR_(A)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(S)]_(n), orR_(S)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(A)]_(n), as previously described.The substrate may be a (co)polymeric film or a moisture sensitive devicesuch as a moisture sensitive electronic device. The moisture sensitivedevice can be, for example, an organic, inorganic, or hybrid organicinorganic semiconductor device including, for example, a display devicesuch as an organic light emitting diode (OLED), electrochromic,electrophoretic or quantum dot display; an OLED or otherelectroluminescent solid state lighting device, and the like.

In some exemplary embodiments of the process, the at least one urea(multi)-(meth)acrylate (multi)-silane precursor compound undergoes achemical reaction to form the protective (co)polymer layer at least inpart on the oxide layer. Optionally, the chemical reaction is selectedfrom a free radical polymerization reaction, and a hydrolysis reaction.In any of the foregoing articles, each hydrolysable group Y isindependently selected from an alkoxy group, an acetate group, anaryloxy group, and a halogen. In some particular exemplary embodimentsof the foregoing articles, at least some of the hydrolysable groups Yare alkoxy groups.

In another presently preferred exemplary embodiment, the disclosuredescribes a process for making a barrier film, the process comprising:(a) vapor depositing and curing a base (co)polymer layer onto a majorsurface of a (co)polymer film substrate; (b) vapor depositing an oxidelayer on the base (co)polymer layer; and (c) vapor depositing and curingonto the oxide layer a protective (co)polymer layer, the protective(co)polymer layer comprising a (co)polymer formed as the reactionproduct of at least one of the foregoing urea (multi)-urethane(meth)acrylate-silane precursor compounds of the formulaR_(A)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(S)]_(n), orR_(S)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(A)]_(n), as previously described.The barrier film may be advantageously applied to a moisture sensitivedevice.

As described further below, the barrier assembly can be depositeddirectly on a (co)polymer film substrate, or a substrate that includes amoisture sensitive device, a process often referred to as directdeposition or direct encapsulation. Exemplary direct depositionprocesses and barrier assemblies or described in U.S. Pat. No. 5,654,084(Affinito); U.S. Pat. No. 6,522,067 (Graff et al.); U.S. Pat. No.6,548,912 (Graff et al.); U.S. Pat. No. 6,573,652 (Graff et al.); andU.S. Pat. No. 6,835,950 (Brown et al.).

In some exemplary embodiments, flexible electronic devices can beencapsulated directly with the methods described herein. For example,the devices can be attached to a flexible carrier substrate, and a maskcan be deposited to protect electrical connections from the inorganiclayer(s), (co)polymer layer(s), or other layer(s)s during theirdeposition. The inorganic layer(s), (co)polymeric layer(s), and otherlayer(s) making up the multilayer barrier assembly can be deposited asdescribed elsewhere in this disclosure, and the mask can then beremoved, exposing the electrical connections.

In one exemplary direct deposition or direct encapsulation embodiment,the moisture sensitive device is a moisture sensitive electronic device.The moisture sensitive electronic device can be, for example, anorganic, inorganic, or hybrid organic/inorganic semiconductor deviceincluding, for example, a photovoltaic device such as a copper indiumgallium (di)selenide (CIGS) solar cell; a display device such as anorganic light emitting display (OLED), electrochromic display,electrophoretic display, or a liquid crystal display (LCD) such as aquantum dot LCD display; an OLED or other electroluminescent solid statelighting device, or combinations thereof and the like.

Examples of suitable processes for making a multilayer barrier assemblyand suitable transparent multilayer barrier coatings can be found, forexample, in U.S. Pat. No. 5,440,446 (Shaw et al.); U.S. Pat. No.5,877,895 (Shaw et al.); U.S. Pat. No. 6,010,751 (Shaw et al.); and U.S.Pat. No. 7,018,713(Padiyath et al.). In one presently preferredembodiment, the barrier film can be fabricated by deposition of thevarious layers onto the substrate, in a roll-to-roll vacuum chambersimilar to the system described in U.S. Pat. Nos. 5,440,446 (Shaw etal.) and U.S. Pat. No. 7,018,713 (Padiyath, et al.).

It is presently preferred that the base polymer layer 14 is formed byflash evaporation and vapor deposition followed by crosslinking in situ,e.g., as described in U.S. Pat. No. U.S. Pat. No. 4,696,719 (Bischoff),U.S. Pat. No. 4,722,515 (Ham), U.S. Pat. No. 4,842,893 (Yializis etal.), U.S. Pat. No. 4,954,371 (Yializis), U.S. Pat. No. 5,018,048 (Shawet al.), U.S. Pat. No. 5,032,461(Shaw et al.), U.S. Pat. No. 5,097,800(Shaw et al.), U.S. Pat. No. 5,125,138 (Shaw et al.), U.S. Pat. No.5,440,446 (Shaw et al.), U.S. Pat. No. 5,547,908 (Furuzawa et al.), U.S.Pat. No. 6,045,864 (Lyons et al.), U.S. Pat. No. 6,231,939 (Shaw et al.and 6,214,422 (Yializis); and in PCT International Publication No. WO00/26973 (Delta V Technologies, Inc.).

The vapor deposition process is generally limited to compositions thatare pumpable (liquid-phase with an acceptable viscosity); that can beatomized (form small droplets of liquid), flash evaporated (high enoughvapor pressure under vacuum conditions), condensable (vapor pressure,molecular weight), and can be cross-linked in vacuum (molecular weightrange, reactivity, functionality).

FIG. 2 is a diagram of a system 22, illustrating a process for making abarrier assembly in an article or film 10. System 22 is contained withinan inert environment and includes a chilled drum 24 for receiving andmoving the substrate 12 (FIG. 1), as represented by a film 26, therebyproviding a moving web on which to form the barrier layers. Preferably,an optional nitrogen plasma treatment unit 40 may be used to plasmatreat or prime film 26 in order to improve adhesion of the base(co)polymer layer 14 (FIG. 1) to substrate 12 (FIG. 1). An evaporator 28applies a base (co)polymer precursor, which is cured by curing unit 30to form base (co)polymer layer 14 (FIG. 1) as drum 24 advances the film26 in a direction shown by arrow 25. An oxide sputter unit 32 applies anoxide to form layer 16 (FIG. 1) as drum 24 advances film 26.

For additional alternating oxide layers 16 and protective (co)polymerlayers 18, drum 24 can rotate in a reverse direction opposite arrow 25and then advance film 26 again to apply the additional alternating base(co)polymer and oxide layers, and that sub-process can be repeated foras many alternating layers as desired or needed. Once the base(co)polymer and oxide are complete, drum 24 further advances the film,and evaporator 36 deposits on oxide layer 16, the urea(multi)-(meth)acrylate (multi)-silane compound (as described above),which is reacted or cured to form protective (co)polymer layer 18 (FIG.1). In certain presently preferred embodiments, reacting the urea(multi)-(meth)acrylate (multi)-silane compound to form a protective(co)polymer layer 18 on the oxide layer 16 occurs at least in part onthe oxide layer 16.

Optional evaporator 34 may be used additionally to provide otherco-reactants or co-monomers (e.g. additional protective (co)polymercompounds) which may be useful in forming the protective (co)polymerlayer 18 (FIG. 1). For additional alternating oxide layers 16 andprotective (co)polymer layers 18, drum 24 can rotate in a reversedirection opposite arrow 25 and then advance film 26 again to apply theadditional alternating oxide layers 16 and protective (co)polymer layers18, and that sub-process can be repeated for as many alternating layersor dyads as desired or needed.

The oxide layer 16 can be formed using techniques employed in the filmmetalizing art such as sputtering (e.g., cathode or planar magnetronsputtering), evaporation (e.g., resistive or electron beam evaporation),chemical vapor deposition, plating and the like. In one aspect, theoxide layer 16 is formed using sputtering, e.g., reactive sputtering.Enhanced barrier properties have been observed when the oxide layer isformed by a high energy deposition technique such as sputtering comparedto lower energy techniques such as conventional chemical vapordeposition processes. Without being bound by theory, it is believed thatthe enhanced properties are due to the condensing species arriving atthe substrate with greater kinetic energy as occurs in sputtering,leading to a lower void fraction as a result of compaction.

In some exemplary embodiments, the sputter deposition process can usedual targets powered by an alternating current (AC) power supply in thepresence of a gaseous atmosphere having inert and reactive gasses, forexample argon and oxygen, respectively. The AC power supply alternatesthe polarity to each of the dual targets such that for half of the ACcycle one target is the cathode and the other target is the anode. Onthe next cycle the polarity switches between the dual targets. Thisswitching occurs at a set frequency, for example about 40 kHz, althoughother frequencies can be used. Oxygen that is introduced into theprocess forms oxide layers on both the substrate receiving the inorganiccomposition, and also on the surface of the target. The dielectricoxides can become charged during sputtering, thereby disrupting thesputter deposition process. Polarity switching can neutralize thesurface material being sputtered from the targets, and can provideuniformity and better control of the deposited material.

In further exemplary embodiments, each of the targets used for dual ACsputtering can include a single metal or nonmetal element, or a mixtureof metal and/or nonmetal elements. A first portion of the oxide layerclosest to the moving substrate is deposited using the first set ofsputtering targets. The substrate then moves proximate the second set ofsputtering targets and a second portion of the oxide layer is depositedon top of the first portion using the second set of sputtering targets.The composition of the oxide layer changes in the thickness directionthrough the layer.

In additional exemplary embodiments, the sputter deposition process canuse targets powered by direct current (DC) power supplies in thepresence of a gaseous atmosphere having inert and reactive gasses, forexample argon and oxygen, respectively. The DC power supplies supplypower (e.g. pulsed power) to each cathode target independent of theother power supplies. In this aspect, each individual cathode target andthe corresponding material can be sputtered at differing levels ofpower, providing additional control of composition through the layerthickness. The pulsing aspect of the DC power supplies is similar to thefrequency aspect in AC sputtering, allowing control of high ratesputtering in the presence of reactive gas species such as oxygen.Pulsing DC power supplies allow control of polarity switching, canneutralize the surface material being sputtered from the targets, andcan provide uniformity and better control of the deposited material.

In one particular exemplary embodiment, improved control duringsputtering can be achieved by using a mixture, or atomic composition, ofelements in each target, for example a target may include a mixture ofaluminum and silicon. In another embodiment, the relative proportions ofthe elements in each of the targets can be different, to readily providefor a varying atomic ratio throughout the oxide layer. In oneembodiment, for example, a first set of dual AC sputtering targets mayinclude a 90/10 mixture of silicon and aluminum, and a second set ofdual AC sputtering targets may include a 75/25 mixture of aluminum andsilicon. In this embodiment, a first portion of the oxide layer can bedeposited with the 90%Si/10%Al target, and a second portion can bedeposited with the 75%Al/25%Si target. The resulting oxide layer has agradient composition that changes from about 90% Si to about 25% Si (andconversely from about 10% Al to about 75% Al) through the thickness ofthe oxide layer.

In typical dual AC sputtering, homogeneous oxide layers are formed, andbarrier performance from these homogeneous oxide layers suffer due todefects in the layer at the micro and nano-scale. One cause of thesesmall scale defects is inherently due to the way the oxide grows intograin boundary structures, which then propagate through the thickness ofthe film. Without being bound by theory, it is believed several effectscontribute to the improved barrier properties of the gradientcomposition barriers described herein. One effect can be that greaterdensification of the mixed oxides occurs in the gradient region, and anypaths that water vapor could take through the oxide are blocked by thisdensification. Another effect can be that by varying the composition ofthe oxide materials, grain boundary formation can be disrupted resultingin a microstructure of the film that also varies through the thicknessof the oxide layer. Another effect can be that the concentration of oneoxide gradually decreases as the other oxide concentration increasesthrough the thickness, reducing the probability of forming small-scaledefect sites. The reduction of defect sites can result in a coatinghaving reduced transmission rates of water permeation.

In some exemplary embodiments, exemplary films can be subjected topost-treatments such as heat treatment, ultraviolet (UV) or vacuum UV(VUV) treatment, or plasma treatment. Heat treatment can be conducted bypassing the film through an oven or directly heating the film in thecoating apparatus, e.g., using infrared heaters or heating directly on adrum. Heat treatment may for example be performed at temperatures fromabout 30° C. to about 200° C., about 35° C. to about 150° C., or about40° C. to about 70° C.

Other functional layers or coatings that can be added to the inorganicor hybrid film include an optional layer or layers to make the film morerigid. The uppermost layer of the film is optionally a suitableprotective layer, such as optional inorganic layer 20. If desired, theprotective layer can be applied using conventional coating methods suchas roll coating (e.g., gravure roll coating) or spray coating (e.g.,electrostatic spray coating), then cross-linked using, for example, UVradiation. The protective layer can also be formed by flash evaporation,vapor deposition and cross-linking of a monomer as described above.Volatilizable (meth)acrylate monomers are suitable for use in such aprotective layer. In a specific embodiment, volatilizable (meth)acrylatemonomers are employed.

Methods of Using Barrier Films

In a further aspect, the disclosure describes methods of using a barrierfilm made as described above in an article selected from a solid statelighting device, a display device, and combinations thereof. Exemplarysolid state lighting devices include semiconductor light-emitting diodes(SLEDs, more commonly known as LEDs), organic light-emitting diodes(OLEDs), or polymer light-emitting diodes (PLEDs). Exemplary displaydevices include liquid crystal displays, OLED displays, and quantum dotdisplays.

Exemplary LEDs are described in U.S. Pat. No. 8,129,205. Exemplary OLEDsare described in U.S. Pat. Nos. 8,193,698 and 8,221,176. Exemplary PLEDsare described in U.S. Pat. No. 7,943,062.

Unexpected Results and Advantages

Exemplary barrier assemblies in articles or films of the presentdisclosure have a number of applications and advantages in the display,lighting, and electronic device markets as flexible replacements forglass encapsulating materials. Thus, certain exemplary embodiments ofthe present disclosure provide barrier assemblies in articles or filmswhich exhibit improved moisture resistance when used in moisture barrierapplications. In some exemplary embodiments, the barrier assembly in anarticle or film can be deposited directly on a substrate that includes amoisture sensitive device, a process often referred to as directencapsulation.

The moisture sensitive device can be a moisture sensitive electronicdevice, for example, an organic, inorganic, or hybrid organic/inorganicsemiconductor device including, for example, a photovoltaic device suchas a CIGS; a display device such as an OLED, electrochromic, or anelectrophoretic display; an OLED or other electroluminescent solid statelighting device, or others. Flexible electronic devices can beencapsulated directly with a gradient composition oxide layer. Forexample, the devices can be attached to a flexible carrier substrate,and a mask can be deposited to protect electrical connections from theoxide layer deposition. A base (co)polymer layer and the oxide layer canbe deposited as described above, and the mask can then be removed,exposing the electrical connections.

Exemplary embodiments of the disclosed methods can enable the formationof barrier assemblies in articles or films that exhibit superiormechanical properties such as elasticity and flexibility yet still havelow oxygen or water vapor transmission rates. The assemblies in articlesor films have at least one inorganic or hybrid organic/oxide layer orcan have additional inorganic or hybrid organic/oxide layers. In oneembodiment, the disclosed barrier assemblies in articles or films canhave inorganic or hybrid layers alternating with organic compound, e.g.,(co)polymer layers. In another embodiment, the barrier assemblies inarticles or films can include an inorganic or hybrid material and anorganic compound.

Substrates having a barrier assembly in an article or film formed usingthe disclosed method can have an oxygen transmission rate (OTR) lessthan about 1 cc/m²-day, less than about 0.5 cc/m²-day, or less thanabout 0.1 cc/m²-day. Substrates having a barrier assembly in an articleor film formed using the disclosed method can have an water vaportransmission rate (WVTR) less than about 10 cc/m²-day, less than about 5cc/m²-day, or less than about 1 cc/m²-day.

Exemplary embodiments of barrier assemblies in articles and barrierfilms according to the present disclosure are preferably transmissive toboth visible and infrared light. The term “transmissive to visible andinfrared light” as used herein can mean having an average transmissionover the visible and infrared portion of the spectrum of at least about75% (in some embodiments at least about 80, 85, 90, 92, 95, 97, or 98%)measured along the normal axis. In some embodiments, the visible andinfrared light-transmissive assembly has an average transmission over arange of 400 nm to 1400 nm of at least about 75% (in some embodiments atleast about 80, 85, 90, 92, 95, 97, or 98%). Visible and infraredlight-transmissive assemblies are those that do not interfere withabsorption of visible and infrared light, for example, by photovoltaiccells. In some embodiments, the visible and infrared light-transmissiveassembly has an average transmission over a range wavelengths of lightthat are useful to a photovoltaic cell of at least about 75% (in someembodiments at least about 80, 85, 90, 92, 95, 97, or 98%). The firstand second (co)polymeric film substrates, pressure sensitive adhesivelayer, and barrier film can be selected based on refractive index andthickness to enhance transmission to visible and infrared light.

Exemplary embodiments of barrier assemblies in articles and barrierfilms according to the present disclosure are typically flexible. Theterm “flexible” as used herein with respect to a barrier film refers tobeing capable of being formed into a roll. In some barrier filmembodiments, the term “flexible” refers to being capable of being bentaround a roll core with a radius of curvature of up to 7.6 centimeters(cm) (3 inches), in some embodiments up to 6.4 cm (2.5 inches), 5 cm (2inches), 3.8 cm (1.5 inch), or 2.5 cm (1 inch). In some embodiments, theflexible assembly can be bent around a radius of curvature of at least0.635 cm (¼ inch), 1.3 cm (½ inch) or 1.9 cm (¾ inch).

Exemplary barrier assemblies in articles and barrier films according tothe present disclosure generally do not exhibit delamination or curlthat can arise from thermal stresses or shrinkage in a multilayerstructure. Herein, curl is measured for barrier films using a curl gaugedescribed in “Measurement of Web Curl” by Ronald P. Swanson presented inthe 2006 AWEB conference proceedings (Association of IndustrialMetallizers, Coaters and Laminators, Applied Web Handling ConferenceProceedings, 2006). According to this method curl can be measured to theresolution of 0.25 m⁻¹ curvature. In some embodiments, barrier filmsaccording to the present disclosure exhibit curls of up to 7, 6, 5, 4,or 3 m⁻¹. From solid mechanics, the curvature of a beam is known to beproportional to the bending moment applied to it. The magnitude ofbending stress is in turn is known to be proportional to the bendingmoment. From these relations the curl of a sample can be used to comparethe residual stress in relative terms. Barrier films also typicallyexhibit high peel adhesion to EVA, and other common encapsulants forphotovoltaics, cured on a substrate.

The properties of the barrier films disclosed herein typically aremaintained even after high temperature and humidity aging.

Exemplary embodiments of the present disclosure have been describedabove and are further illustrated below by way of the followingExamples, which are not to be construed in any way as imposinglimitations upon the scope of the present disclosure. On the contrary,it is to be clearly understood that resort may be had to various otherembodiments, modifications, and equivalents thereof which, after readingthe description herein, may suggest themselves to those skilled in theart without departing from the spirit of the present disclosure and/orthe scope of the appended claims.

EXAMPLES

The following examples are intended to illustrate exemplary embodimentswithin the scope of this disclosure. Notwithstanding that the numericalranges and parameters setting forth the broad scope of the disclosureare approximations, the numerical values set forth in the specificexamples are reported as precisely as possible. Any numerical value,however, inherently contains certain errors necessarily resulting fromthe standard deviation found in their respective testing measurements.At the very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claims, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

Materials Used

The following materials, abbreviations, and trade names are used in theExamples:

90% Si/10% Al targets were obtained from Materion Advanced Chemicals,Inc., Albuquerque, N Mex.

ETFE film: Ethylene-tetrafluoroethylene film available from St. GobainPerformance Plastics, Wayne, N.J. under the trade name “NORTON® ETFE.”

Solvents and other reagents used were obtained from Sigma-AldrichChemical Company (Milwaukee, Wis.), unless otherwise specified.

Table 1 lists the materials used to prepare urea (multi)-urethane(meth)acrylate-silane precursor compounds according to the foregoingdisclosure:

TABLE 1 Materials Used in the Examples Trade Name or Material TypeAcronym Description (Meth)acrylated BEI 1,1-bis(acryloyloxymethyl) ethylisocyanate material w/ available from CBC America Corp. isocyanate(Commack, NY) functionality (Meth)acrylated IEA Isocyanatoethyl acrylateavailable from CBC material w/ America Corp. (Commack, NY) isocyanatefunctionality (Meth)acrylated IEM Isocyanatoethyl methacrylate availablefrom material w/ CBC America Corp. (Commack, NY) isocyanatefunctionality Catalyst DBTDL Dibutyltin dilaurate available from SigmaAldrich (Milwaukee, WI) AHPM 3-acryloxy-2-hydroxy-propyl methacrylateAmino alcohol MEA N-methyl ethanolamine available from Sigma Aldrich(Milwaukee, WI) Amino alcohol DEA Diethanolamine available from SigmaAldrich (Milwaukee, WI) Amino alcohol AEPD2-amino-2-ethyl-1,3-propanediol available from Sigma Aldrich (Milwaukee,WI) Solvent CF Chloroform available from EMD Chemicals, (Gibbstown, NJ)Solvent MEK Methyl ethyl ketone available from EMD Chemicals, Inc.Silane-functional Geniosil GF 3-trimethoxysilylpropyl isocyanateavailable isocyanate 40 from Wacker Silicones (Adrian, MI)Silane-functional NANA 3-triethoxysilylpropyl isocyanateisocyanateisocyanate available from Gelest, Inc. (Morrisville, PA) CyclicAzasilane Cyclic AZA N-n-butyl-aza-2,2-dimethoxysilacylopentane Silaneavailable from Gelest, Inc. (Morrisville, PA) 1932.4

Synthesis Of Urea (Multi)-Urethane (Meth)Acrylate-Silane PrecursorCompounds

Preparatory Example 1

A 100 mL round bottom flask equipped with stirbar was charged with 11.79g (0.157 mol) of N-methyl ethanolamine and placed in an ice bath. Via apressure equalizing addition funnel, 24.36 g (0.157 mol) of IEM wasadded over the course of 30 min. A sample of this intermediate was takenfor Fourier Transform Infrared (FTIR) spectroscopic analysis, and noisocyanate peak at 2265 cm⁻¹ was observed.

A 250 mL round bottom flask was charged with 35.26 g (0.143 mol) ofisocyanatopropyltriethoxysilane and 840 microliters of a 10% solution ofdibutyltin dilaurate (DBTDL) in methyl ethyl ketone (representing 2000ppm of DBTDL in the mixture) and placed in a 55° C. oil bath. Then 33.3g (0.144 mol) of the intermediate formed in the step above wastransferred to an addition funnel and added to the 250 mL flask over 2hour and 15 minutes. Analysis by FTIR showed a small isocyanate peak at2265 cm⁻¹. The addition funnel was found to contain 0.37 g of theintermediate, so at 2 hours and 30 min into the reaction, an additional0.37 g of the intermediate was added to the reaction via pipette.Analysis by FTIR 10 min after this addition showed no isocyanate peak at2265 cm⁻¹, and the product was removed and bottled:

Preparatory Example 2

A 100 mL round bottom flask equipped with stirbar was charged with 13.17g (0.1105 mol) of 2-amino-2-ethyl-1,3-propanediol and placed in an icebath. Via a pressure equalizing addition funnel, 17.14 g (0.1105 mol) ofIEM was added over the course of 30 min. A urea diol intermediate in theform of a thick oil was formed. Its viscosity necessitated that it belightly heated for transfer and addition at the next step discussedbelow.

A 250 mL round bottom flask was charged with 43.85 g (0.177 mol) ofisocyanatopropyltriethoxysilane and 873 microliters of a 10% solution ofDBTDL in methyl ethyl ketone (representing 1000 ppm of DBTDL in themixture) and placed in a 55° C. oil bath. Then 24.56 g (0.0895 mol,0.179 eq) of urea diol intermediate from the first step above wastransferred to an addition funnel and added to the 250 mL flask over thecourse of 2 hours, followed by addition of 0.1 g more of the urea diolintermediate to the flask. The reaction was allowed to proceed for 20hours, whereupon analysis by FTIR showed no isocyanate peak at 2265cm⁻¹. The product was then removed and bottled:

Preparatory Example 3

A 100 mL round bottom flask equipped with stirbar was charged with 11.84g (0.1126 mol) of diethanolamine and placed in an ice bath. Via apressure equalizing addition funnel, 17.47 g (0.1126 mol) of IEM wasadded over the course of 30 min. A urea diol intermediate in the form ofa thick oil was formed, somewhat less viscous than the intermediateformed in Example 2.

A 250 mL round bottom flask was charged with 43.95 g (0.1777 mol) ofisocyanatopropyltriethoxysilane and enough of a 10% solution of DBTDL inmethyl ethyl ketone to represent 1000 ppm of DBTDL in the mixture, andplaced in a 55° C. oil bath. Then 23.36 g (0.0888 mol, 0.1777 eq) ofurea diol intermediate from the first step above was transferred to anaddition funnel and added to the 250 mL flask over the course of 2hours, followed by addition of 0.1 g more of the urea diol intermediateto the flask. The reaction was allowed to proceed for 20 hours,whereupon analysis by FTIR showed no isocyanate peak at 2265 cm⁻¹. Theproduct was then removed and bottled:

Preparatory Example 4

A 100 mL round bottom flask equipped with overhead stirrer was chargedwith 16.32 g (0.116 mol) of IEA and placed in water bath at roomtemperature. Using an addition funnel, 8.68 g (0.116 mol) ofN-methylethanolamine was added over 20 min. At 30 min time, FTIRanalysis of the reaction showed no isocyanate peak. The flask was placedin a 55° C. oil bath, and to the flask was added 189 microliters of a10% solution of DBTDL in MEK (representing 300 ppm of DBTDL in themixture), followed by 28.60 g (0.116 mol) of 3-triethoxysilylpropylisocyanate, via addition funnel over 20 min. After 24 hour of heating, asample was taken for FTIR analysis, and there was still a sizableisocyanate peak at 2265 cm⁻¹. The reaction was at allowed to continue at55° C. for another 24 hours. A second sample was taken to be analyzed byFTIR, and this time the output showed no isocyanate peak. The productwas then removed and bottled:

Preparatory Example 5

A 100 mL round bottom flask equipped with overhead stirrer was chargedwith 11.72 g (0.083 mol) of IEA, and 6.24 g (0.083 mol)N-methyl-ethanolamine was added at room temperature over the course of20 minutes. After the reaction was allowed to run for 1.5 hours, andsample was taken for FTIR analysis. The intermediate showed noisocyanate peak.

The flask was then placed in a 55° C. oil bath and further charged with206 microliters of 10% DBTDL in MEK (representing 500 ppm of DBTDL inthe mixture). To the flask was added 17.05 g (0.083 mol) of3-trimethoxysilylpropyl isocyanate over the course of 20 min. Thereaction was allowed to run for 16 hours, whereupon a sample was takenfor FTIR analysis. The sample showed no isocyanate peak and the productwas isolated and bottled:

Preparatory Example 6

A 100 mL 3 necked roundbottom flask equipped with overhead stirrer wasfurther equipped with two pressure equalizing addition funnels, onestoppered and one under dry air.

One funnel was charged with 10.10 (0.096 mol, 105.14 MW) ofdiethanolamine, and 13.8 g of chloroform. The other funnel was chargedwith 13.55 g (0.096 mol) of IEA, 10.79 g of chloroform, and 367microliters of 10% DBTDL in MEK solution (representing 500 ppm of DBTDLin the mixture).

The flask was placed in an ice bath, and the equi-volume (˜19 mL each)contents of the two funnels, were dispensed into the reaction flask atabout the same volume rate over about 30 min. The content of each funnelwas washed into the reaction with about 4.5 g chloroform for eachfunnel. The solvent was then evaporated away on a rotary evaporator at65° C., leaving an intermediate acrylate urea diol.

A 100 mL round bottom flask equipped with overhead stirrer was chargedwith 10.04 g (0.0408 mol, 0.0815 equivalents) of the intermediateacrylate urea diol; 16.72 g (0.0815 mol) of 3-trimethoxysilylpropylisocyanate; and 60 microliters of 10% solution of DBTDL in MEK(representing 2353 ppm of DBTDL in the mixture). The flask was placedunder dry air at 55° C. overnight. The product was then isolated andbottled:

Preparatory Example 7

A 250 mL, 3 necked round bottom flask equipped with overhead stirrer wascharged with 10 g of ethyl acetate, and 200 microliters of 10% DBTDL inMEK, and placed in a room temperature water bath. A dropping funnelcharged with 25.01 g (0.1045 mol) of BEI was put into one neck of theflask, and a dropping funnel charged with 7.85 g (0.1045 mol) ofN-methylethanolamine and 10.86 g of ethyl acetate, enough to make bothdropping funnels have the same approximate volume was placed in theother neck of the flask. Simultaneous addition of both the BEI and theN-methylethanolamine was done at the same drip rate over about 30 min.At 1 hour, a sample was taken for FTIR analysis, and the sample showedno isocyanate peak.

An aliquot was removed from the reaction for NMR analysis. To theremaining 31.39 g solids of product (0.0999 mol) in ethyl acetate wasadded in one portion 20.50 g (0.0999 mol) of3-isocyanatopropyltrimethoxysilane, 110 microliters of 10% DBTDL in MEK,and the reaction was heated at 55° C. under dry air for about 5.5 hours.At that time a sample was taken for FTIR analysis, and again there wasno isocyanate peak. The contents of the flask were concentrated on arotary evaporator to isolate the neat product:

Preparatory Example 8

A 250 mL, 3 necked, round bottom flask equipped with overhead stirrerwas charged with 10 g of chloroform and 205 microliters of 10% DBTDL inMEK solution, and placed in a room temperature water bath. A droppingfunnel charged with 23.92 g (0.100 mol) of BEI was put into one neck ofthe flask, and a dropping funnel charged with 10.51 g (0.100 mol) ofdiethanolamine and enough chloroform to make both dropping funnels havethe same approximate volume was placed in the other neck of the flask.Next simultaneous addition of both the BEI and the diethanolamine wasdone at the same drip rate over about 30 min. At 1.5 hours, each funnelwas rinsed into the flask with about 1 mL of chloroform. At about 2 houra sample was taken for FTIR analysis, and the reaction showed noisocyanate peak. The total weight of the reaction product was 58.1 g(solids 34.43, chloroform 24.27 g).

An aliquot was removed from the intermediate product for NMR analysis.To the remaining 56.68 g of intermediate product, which was 96.56% byweight of the original amount of product and solvent, was added in oneportion 39.64 g (0.19312 mol) of 3-isocyanatopropyltrimethoxysilane. Thereaction was heated at 55° C. under dry air for about 8 hours, and leftat for about 40 hours at room temperature at which time a sample wastaken for FTIR analysis. This analysis showed no isocyanate peak. Thecontents of the flask were concentrated on a rotary evaporator toisolate the neat product:

Preparatory Example 9

A 250 mL round bottom flask equipped with overhead stirrer was chargedwith 34.10 g (0.166 mol) 3-trimethoxysilylpropyl isocyanate, placed in aroom temperature water bath, and 6.24 g (0.083 mol)N-methyl-ethanolamine was added at room temperature over the course of20 minutes. After the reaction was allowed to run for 1.0 hours, andsample was taken for FTIR analysis. The intermediate showed noisocyanate peak.

The flask was then placed in a 55° C. oil bath and further charged withone drop of DBTDL. To the flask was added 23.44 g (0.166 mol) IEA overthe course of 20 min. The reaction was allowed to run for 16 hours,whereupon a sample was taken for FTIR analysis. The sample showed noisocyanate peak and the product was isolated and bottled:

Composite Barrier Assembly and Barrier Film Preparation

Examples of multilayer composite barrier assemblies and barrier filmswere made on a vacuum coater similar to the coater described in U.S.Pat. No. 5,440,446 (Shaw et al.) and U.S. Pat. No. 7,018,713 (Padiyath,et al.).

Comparative Example 10 and Examples 11 through 14 below relate toforming simulated solar modules which were subjected to under conditionsdesigned to simulate aging in an outdoor environment and then subjectedto a peel adhesion test to determine if the urea (multi)-urethane(meth)acrylate-silane precursor compounds of the above PreparatoryExamples were effective in improving peel adhesion. Some procedurescommon to all these Examples are presented first.

Multilayer composite barrier films according to the examples below werelaminated to a 0.05 mm thick ethylene tetrafluoroethylene (ETFE) filmcommercially available as NORTON® ETFE from St. Gobain PerformancePlastics (Wayne, N.J.), using a 0.05 mm thick pressure sensitiveadhesive (PSA) commercially available as 3M OPTICALLY CLEAR ADHESIVE8172P from 3M Company (St. Paul, Minn.).

The laminated barrier sheets formed in each Example below was thenplaced atop a 0.14 mm thick polytetrafluoroethylene (PTFE) coatedaluminum-foil commercially available commercially as 8656K61, fromMcMaster-Carr, Inc. (Santa Fe Springs, Calif.) with 13 mm widedesiccated edge tape commercially available as SOLARGAIN Edge Tape SETLP01″ from Truseal Technologies, Inc. (Solon, Ohio) placed around theperimeter of the foil between the barrier sheet and the PTFE.

A 0.38 mm thick encapsulant film commercially available as JURASOL fromJuraFilms, Inc. (Downer Grove, Ill.) and an additional layer of thelaminated barrier sheet were placed on the backside of the foil with theencapsulant between the barrier sheet and the foil. The multi-componentconstructions were vacuum laminated at 150° C. for 12 min.

Test Methods

Aging Test

Some of the laminated constructions described above were aged for 250hrs and 500 hours in an environmental chamber set to conditions of 85°C. and 85% relative humidity.

T-peel adhesion test

Unaged and aged barrier sheets were cut away from the PTFE surface anddivided into 1.0 inch (25.4 mm) wide strips for adhesion testing usingthe ASTM D1876-08 T-peel test method. The samples were peeled by a peeltester commercially available as INISIGHT 2 SL equipped with TESTWORKS 4software commercially available from MTS, Inc. (Eden Prairie, Minn.). Apeel rate of 10 in/min (25.4 cm/min) was used. The reported adhesionvalue in Table II below is the average of 4 peel measurements.

Example 10 (Comparative)

This example is comparative in the sense that no urea (multi)-urethane(meth)acrylate-silane precursor compounds as described in PreparatoryExamples 1 through 7 were used. A polyetheylene teraphthalate (PET)substrate film was covered with a stack of an acrylate smoothing layer,an inorganic silicon aluminum oxide (SiAlOx) barrier and an acrylateprotective layer. The individual layers were formed as follows:

(Deposition of the (Meth)Acrylate Smoothing Layer)

A 305 meter long roll of 0.127 mm thick by 366 mm wide PET filmcommercially available XST 6642 from Dupont of Wilmington, Del. wasloaded into a roll-to-roll vacuum processing chamber. The chamber waspumped down to a pressure of 1×10⁻⁵ Torr. The web speed was maintainedat 4.8 meter/min while maintaining the backside of the film in contactwith a coating drum chilled to −10° C.

With the film in contact with the drum, the film surface was treatedwith a nitrogen plasma at 0.02 kW of plasma power. The film surface wasthen coated with tricyclodecane dimethanol diacrylate commerciallyavailable as SR-833S from Sartomer USA, LLC, Exton, Pa.). Morespecifically, the diacrylate was degassed under vacuum to a pressure of20 mTorr prior to coating, loaded into a syringe pump, and pumped at aflow rate of 1.33 mL/min through an ultrasonic atomizer operated at afrequency of 60 kHz into a heated vaporization chamber maintained at260° C. The resulting monomer vapor stream condensed onto the filmsurface and was electron beam cross-linked using a multi-filamentelectron-beam cure gun operated at 7.0 kV and 4 mA to form a 720 nmacrylate layer.

(Deposition of the Inorganic Silicon Aluminum Oxide (SiAlOx) Barrier)

Immediately after the acrylate deposition and with the film still incontact with the drum, a SiAlOx layer was sputter-deposited atop theacrylate-coated web surface. Two alternating current (AC) power supplieswere used to control two pairs of cathodes; with each cathode housingtwo 90% Si/10% Al targets commercially available from Materion ofAlbuquerque, N Mex.. During sputter deposition, the voltage signal fromeach power supply was used as an input for aproportional-integral-differential control loop to maintain apredetermined oxygen flow to each cathode. The AC power suppliessputtered the 90% Si/10% Al targets using 5000 watts of power, with agas mixture containing 450 sccm argon and 63 sccm oxygen at a sputterpressure of 3.5 millitorr. This provided a 30 nm thick SiAlOx layerdeposited atop the acrylate discussed above.

(Deposition of the (Meth)acrylate Protective Layer)

Immediately after the SiAlOx layer deposition and with the film still incontact with the drum, an acrylate protective layer second was coatedand cross-linked on the same web generally using the same conditions asfor the deposition of the smoothing layer, but with the followingexceptions. The electron beam cross-linking was carried out using amulti-filament electron-beam cure gun operated at 7 kV and 5 mA. Thisprovided a 720 nm thick acrylate layer atop Layer 2.

The resulting three layer stack on the (co)polymeric substrate exhibitedan average spectral transmission T_(vis) of 87%, determined by averagingthe percent transmission T between 400 nm and 700 nm, measured at a θangle of incidence. A water vapor transmission rate (WVTR) was measuredin accordance with ASTM F-1249 at 50° C. and 100% relative humidity (RH)using MOCON PERMATRAN-W® Model 700 WVTR testing system commerciallyavailable from MOCON, Inc, Minneapolis, Minn.). The result was below the0.005 g/m²/day lower detection limit rate of the apparatus.

The resulting three layer stack was used to form a simulated solarmodule construction as discussed in the section on general proceduresabove. These simulated solar modules were subjected to accelerated agingaccording to the aging test, and then the T-peel adhesion was assessedas discussed above. The results of the T-peel adhesion test arepresented in Table 2 below.

Example 11

A polyethylene teraphthalate (PET) substrate film was covered with astack of an acrylate smoothing layer, an inorganic silicon aluminumoxide (SiAlOx) barrier and an acrylate protective layer containing theinvention molecules. The individual layers were formed as in ComparativeExample 10 except during the formation of the protective layer, insteadof 100% tricyclodecane dimethanol diacrylate SR-833S being used, amixture of 97% by weight of tricyclodecane dimethanol diacrylate SR-833Sand 3% by weight of the compound synthesized in Preparatory Example 5above was used instead.

The resulting three layer stack on the (co)polymeric substrate exhibitedan average spectral transmission T_(vis)=87% and a WVTR below the 0.005g/m²/day, both tested as described in Preparatory Example 9. Then theresulting three layer stack was used to form a simulated solar moduleconstruction as discussed in the section on general procedures above.These simulated solar modules were subjected to accelerated agingaccording to the aging test, and then the T-peel adhesion was assessedas discussed above. The results of the T-peel adhesion test arepresented in Table 2 below.

Example 12

A polyethylene teraphthalate (PET) substrate film was covered with astack of an acrylate smoothing layer, an inorganic silicon aluminumoxide (SiAlOx) barrier and an acrylate protective layer containing theinvention molecules. The individual layers were formed as in ComparativeExample 10 except during the formation of the protective layer, insteadof 100% tricyclodecane dimethanol diacrylate SR-833S being used, amixture of 97% by weight of tricyclodecane dimethanol diacrylate SR-833Sand 3% by weight of the compound synthesized in Preparatory Example 6above was used instead.

The resulting three layer stack on the (co)polymeric substrate exhibitedan average spectral transmission T_(vis)=87% and a WVTR below the 0.005g/m²/day, both tested as described in Comparative Example 10. Then theresulting three layer stack was used to form a simulated solar moduleconstruction as discussed in the section on general procedures above.These simulated solar modules were subjected to accelerated agingaccording to the aging test, and then the T-peel adhesion was assessedas discussed above. The results of the T-peel adhesion test arepresented in Table 2 below.

Example 13

A polyethylene teraphthalate (PET) substrate film was covered with astack of an acrylate smoothing layer, an inorganic silicon aluminumoxide (SiAlOx) barrier and an acrylate protective layer containing theinvention molecules. The individual layers were formed as in ComparativeExample 10 except during the formation of the protective layer, insteadof 100% tricyclodecane dimethanol diacrylate SR-833S being used, amixture of 97% by weight of tricyclodecane dimethanol diacrylate SR-833Sand 3% by weight of the compound synthesized in Preparatory Example 7above was used instead.

The resulting three layer stack on the (co)polymeric substrate exhibitedan average spectral transmission T_(vis)=87% and a WVTR below the 0.005g/m²/day, both tested as described in Comparative Example 10. Then theresulting three layer stack was used to form a barrier moduleconstruction as discussed in the section on general procedures above.These simulated solar modules were subjected to accelerated agingaccording to the aging test, and then the T-peel adhesion was assessedas discussed above. The results of the T-peel adhesion test arepresented in Table 2 below.

Example 14

A polyethylene teraphthalate (PET) substrate film was covered with astack of an acrylate smoothing layer, an inorganic silicon aluminumoxide (SiAlOx) barrier and an acrylate protective layer containing theinvention molecules. The individual layers were formed as in ComparativeExample 10 except during the formation of the protective layer, insteadof 100% tricyclodecane dimethanol diacrylate SR-833S being used, amixture of 97% by weight of tricyclodecane dimethanol diacrylate SR-833Sand 3% by weight of the compound synthesized in Preparatory Example 8above was used instead.

The resulting three layer stack on the (co)polymeric substrate exhibitedan average spectral transmission T_(vis)=87% and a WVTR below the 0.005g/m²/day, both tested as described in Comparative Example 10. Then theresulting three layer stack was used to form a simulated solar moduleconstruction as discussed in the section on general procedures above.These simulated solar modules were subjected to accelerated agingaccording to the aging test, and then the T-peel adhesion was assessedas discussed above. The results of the T-peel adhesion test arepresented in Table 2 below.

Example 15 (Comparative)

A polyethylene teraphthalate (PET) substrate film was covered with astack of an acrylate smoothing layer, an inorganic silicon aluminumoxide (SiAlOx) barrier and an acrylate protective layer containing thedisclosure molecules. The individual layers were formed as inComparative Example 10 except during the formation of the protectivelayer, instead of 100% tricyclodecane dimethanol diacrylate SR-833Sbeing used, a mixture of 97% by weight of tricyclodecane dimethanoldiacrylate SR-833S and 3% by weight ofN-n-butyl-AZA-2,2-dimethoxysilacyclopentane (commercially available fromGelest, Inc., Morrisville, Pa., under the product code 1932.4) was usedinstead.

The resulting three layer stack on the (co)polymeric substrate exhibitedan average spectral transmission T_(vis)=87% and a WVTR below the 0.005g/m²/day, both tested as described in Comparative Example 10. Then theresulting three layer stack was used to form a simulated solar moduleconstruction as discussed in the section on general procedures above.These simulated solar modules were subjected to accelerated agingaccording to the aging test, and then the T-peel adhesion was assessedas discussed above. The results of the T-peel adhesion test arepresented in Table 2 below.

TABLE 2 T-Peel After T-Peel After T-Peel 250 Hours Aging 1000 HoursAging (N/cm) @ 85° C./85% RH @ 85° C./85% RH Example Initial (N/cm)(N/cm) 10 (Comparative) 0.3 0.1 0.1 11 9.6 10.5 10.7 12 9.4 10.5 10.6 138.2 8.9 0.3 14 0.5 5.3 0.4 15 (Comparative) 6.0 10.1 0.4

While the specification has described in detail certain exemplaryembodiments, it will be appreciated that those skilled in the art, uponattaining an understanding of the foregoing, may readily conceive ofalterations to, variations of, and equivalents to these embodiments.Accordingly, it should be understood that this disclosure is not to beunduly limited to the illustrative embodiments set forth hereinabove.Furthermore, all publications, published patent applications and issuedpatents referenced herein are incorporated by reference in theirentirety to the same extent as if each individual publication or patentwas specifically and individually indicated to be incorporated byreference. Various exemplary embodiments have been described. These andother embodiments are within the scope of the following listing ofembodiments and claims.

The invention claimed is:
 1. An article, comprising: a substrateselected from a (co)polymeric film or an electronic device, theelectronic device further comprising an organic light emitting device(OLED), an electrophoretic light emitting device, a liquid crystaldisplay, a thin film transistor, a photovoltaic device, or a combinationthereof; a base (co)polymer layer on a major surface of the substrate;an oxide layer on the base (co)polymer layer; and a protective(co)polymer layer on the oxide layer, wherein the protective (co)polymerlayer comprises the reaction product of at least one urea(multi)-urethane (meth)acrylate-silane precursor compound of theformula: R_(A)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(S)]_(n), wherein: R_(S) isa silane containing group of the formula —R¹—Si(Y_(p))(R²)_(3-p),wherein: R¹ is a polyvalent alkylene, arylene, alkarylene, or aralkylenegroup, said alkylene, arylene, alkarylene, or aralkylene groupsoptionally containing one or more catenary oxygen atoms, Y is ahydrolysable group, R² is a monovalent alkyl or aryl group, and p is1,2, or 3; R⁴ is H, C₁ to C₆ alkyl, or C₁ to C₆ cycloalkyl; R_(A) is a(meth)acryl group containing group of the formula R¹¹-(A)_(m), furtherwherein: R¹¹ is a polyvalent alkylene, arylene, alkarylene, oraralkylene group, said alkylene, arylene, alkarylene, or aralkylenegroup optionally containing one or more catenary oxygen atom, A is a(meth)acryl containing group of the formula X²—C(O)—(R³)═CH₂,additionally wherein: X² is —O, —S, or —NR³, R³ is independently H, orC₁-C₄, and m=1 to 5, n=2 to
 5. 2. The article of claim 1, wherein eachhydrolysable group Y is independently selected from an alkoxy group, anacetate group, an aryloxy group, and a halogen.
 3. The article of claim2, wherein at least some of the hydrolysable groups Y are alkoxy groups.4. The article of claim 1, further comprising a plurality of alternatinglayers of the oxide layer and the protective (co)polymer layer on thebase (co)polymer layer.
 5. The article of claim 1, wherein the substratecomprises a flexible transparent (co)polymeric film, optionally whereinthe substrate comprises polyethylene terephthalate (PET), polyethylenenapthalate (PEN), heat stabilized PET, heat stabilized PEN,polyoxymethylene, polyvinylnaphthalene, polyetheretherketone, afluoro(co)polymer, polycarbonate, polymethylmethacrylate, poly a-methylstyrene, polysulfone, polyphenylene oxide, polyetherimide,polyethersulfone, polyamideimide, polyimide, polyphthalamide, orcombinations thereof.
 6. The article of claim 1, wherein the base(co)polymer layer comprises an acrylate smoothing layer.
 7. The articleof claim 1, wherein the oxide layer comprises oxides and any one or moreof nitrides, carbides or borides of atomic elements from Groups IIA,IIIA, IVA, VA, VIA, VIIA, IB, or IIB, metals of Groups IIIB, IVB, or VB,rare-earth metals, or combinations thereof.
 8. The article of claim 1,further comprising an oxide layer applied to the protective (co)polymerlayer, optionally wherein the oxide layer comprises silicon aluminumoxide.
 9. An electronic device incorporating the article according toclaim 1, wherein the substrate is the (co)polymer film and the(co)polymer film is applied to a solid state lighting device, a displaydevice, and combinations thereof.
 10. The electronic device according toclaim 9, wherein the solid state lighting device is selected from asemiconductor light-emitting diode device, an organic light-emittingdiode device, and a polymer light-emitting diode device.
 11. Theelectronic device according to claim 9, wherein the display device isselected from a liquid crystal display device, an organic light-emittingdisplay device, and a quantum dot liquid crystal display device.
 12. Aprocess, comprising: (a) applying a base (co)polymer layer to a majorsurface of a substrate selected from a (co)polymeric film or anelectronic device, the electronic device further comprising an organiclight emitting device (OLED), an electrophoretic light emitting device,a liquid crystal display, a thin film transistor, a photovoltaic device,or a combination thereof; (b) applying an oxide layer on the base(co)polymer layer; and (c) depositing on the oxide layer a protective(co)polymer layer, wherein the protective (co)polymer layer comprisesthe reaction product of at least one urea (multi)-urethane(meth)acrylate-silane precursor compound of the formula:R_(A)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(S)]_(n), wherein: R_(A) is a(meth)acryl containing group of the formula R¹¹-(A)_(m), further whereinR¹¹ is an alkylene, arylene, alkarylene, or aralkylene group, saidalkylene, arylene, alkarylene, or aralkylene groups optionallycontaining one or more catenary oxygen atom, A is a (meth)acryl groupcomprising the formula X²—C(O)—C(R³)═CH₂, additionally wherein: X² is—O, R³ is independently H, or CH₃, and n=2 to 5, m=1 to 5 R⁴ is H, C₁ toC₆ alkyl, or C₃to C₆ cycloalkyl; R_(X) is a silane containing group ofthe formula —R¹—Si(Y_(p))(R²)_(3-p), wherein: R¹ is a polyvalentalkylene, arylene, alkarylene, or aralkylene group, said alkylene,arylene, alkarylene, or aralkylene groups optionally containing one ormore catenary oxygen atoms, Y is a hydrolysable group, R² is amonovalent alkyl or aryl group, and p is 1,2, or
 3. 13. The process ofclaim 12, wherein each hydrolysable group Y is independently selectedfrom an alkoxy group, an acetate group, an aryloxy group, and a halogen.14. The process of claim 12, wherein step (a) comprises: (i) evaporatinga base (co)polymer precursor; (ii) condensing the evaporated base(co)polymer precursor onto the substrate; and (iii) curing theevaporated base (co)polymer precursor to form the base (co)polymerlayer.
 15. The process of claim 14, wherein the base (co)polymerprecursor comprises a (meth)acrylate monomer.
 16. The process of claim12, wherein step (b) comprises depositing an oxide onto the base(co)polymer layer to form the oxide layer, wherein depositing isachieved using sputter deposition, reactive sputtering, chemical vapordeposition, or a combination thereof.
 17. The process of claim 12,wherein step (b) comprises applying a layer of an inorganic siliconaluminum oxide to the base (co)polymer layer.
 18. The process of claim12, further comprising sequentially repeating steps (b) and (c) to forma plurality of alternating layers of the protective (co)polymer layerand the oxide layer on the base (co)polymer layer.
 19. The process ofclaim 12, wherein step (c) further comprises at least one ofco-evaporating the at least one urea (multi)-urethane (meth)acrylate-silane precursor compound with a (meth)acrylate compound from a liquidmixture, or sequentially evaporating the at least one urea(multi)-urethane (meth)acrylate-silane precursor compound and a(meth)acrylate compound from separate liquid sources, optionally whereinthe liquid mixture comprises no more than about 10 wt. % of the urea(multi)-urethane (meth)acrylate-silane precursor compound.
 20. Theprocess of claim 19, wherein step (c) further comprises at least one ofco-condensing the urea (multi)-urethane (meth)acrylate-silane precursorcompound with the (meth)acrylate compound onto the oxide layer, orsequentially condensing the urea (multi)-urethane (meth)acrylate-silaneprecursor compound and the (meth)acrylate compound on the oxide layer.